Wetting Properties of Graphene Aerogels

Graphene hydrophobic coatings paved the way towards a new generation of optoelectronic and fluidic devices. Nevertheless, such hydrophobic thin films rely only on graphene non-polar surface, rather than taking advantage of its surface roughness. Furthermore, graphene is typically not self-standing. Differently, carbon aerogels have high porosity, large effective surface area due to their surface roughness, and very low mass density, which make them a promising candidate as a super-hydrophobic material for novel technological applications. However, despite a few works reporting the general super-hydrophobic and lipophilic behavior of the carbon aerogels, a detailed characterization of their wetting properties is still missing, to date. Here, the wetting properties of graphene aerogels are demonstrated in detail. Without any chemical functionalization or patterning of their surface, the samples exhibit a super-lipophilic state and a stationary super-hydrophobic state with a contact angle up to 150 ± 15° and low contact angle hysteresis ≈ 15°, owing to the fakir effect. In addition, the adhesion force of the graphene aerogels in contact with the water droplets and their surface tension are evaluated. For instance, the unique wettability and enhanced liquid absorption of the graphene aerogels can be exploited for reducing contamination from oil spills and chemical leakage accidents

Multifunctional, Self-Cleaning Air Filters Based on Graphene-Enhanced Ceramic Networks

Particulate air pollution is taking a huge toll on modern society, being associated with more than three million deaths per year. In addition, airborne infectious microorganism can spread dangerous diseases, further elevating the problem. A common way to mitigate the risks of airborne particles is by air filtration. However, conventional air filters usually do not provide any functionality beyond particle removal. They are unable to inactivate accumulated contaminants and therefore need periodic maintenance and replacement to remain operational and safe. This work presents a multifunctional, self-cleaning air filtration system which utilizes a novel graphene-enhanced air filter medium (GeFM). The hybrid network of the GeFM combines the passive structure-based air filtration properties of an underlying ceramic network with additional active features based on the functional properties of a graphene thin film. The GeFM is able to capture >95 % of microorganisms and particles larger than 1 $\mu$m and can be repetitively Joule-heated to >300 {\deg}C for several hours without signs of degradation. Hereby, built-up organic particulate matter and microbial contaminants are effectively decomposed, regenerating the GeFM. Additionally, the GeFM provides unique options to monitor the filter's air troughput and loading status during operation. The active features of the GeFM can drastically improve filter life-time and safety, offering great potential for the development of safer and more sustainable air filtration solutions to face the future challenges of air pollution and pandemics.Comment: * Corresponding authors: Prof. Dr. Rainer Adelung ([email protected]) and Dr.-Ing. Fabian Sch\"utt ([email protected]

Overcoming water diffusion limitations in hydrogels via microtubular graphene networks for soft actuators

Hydrogel-based soft actuators can operate in sensitive environments, bridging the gap of rigid machines interacting with soft matter. However, while stimuli-responsive hydrogels can undergo extreme reversible volume changes of up to ~90%, water transport in hydrogel actuators is in general limited by their poroelastic behavior. For poly(N-isopropylacrylamide) (PNIPAM) the actuation performance is even further compromised by the formation of a dense skin layer. Here we show, that incorporating a bioinspired microtube graphene network into a PNIPAM matrix with a total porosity of only 5.4 % dramatically enhances actuation dynamics by up to ~400 % and actuation stress by ~4000 % without sacrificing the mechanical stability, overcoming the water transport limitations. The graphene network provides both untethered light-controlled and electrically-powered actuation. We anticipate that the concept provides a versatile platform for enhancing the functionality of soft matter by combining responsive and two-dimensional materials, paving the way towards designing soft intelligent matter.Comment: Shared First-authorship: Margarethe Hauck and Lena Marie Saur

Microengineered Hollow Graphene Tube Systems Generate Conductive Hydrogels with Extremely Low Filler Concentration

The fabrication of electrically conductive hydrogels is challenging as the introduction of an electrically conductive filler often changes mechanical hydrogel matrix properties. Here, we present an approach for the preparation of hydrogel composites with outstanding electrical conductivity at extremely low filler loadings (0.34 S m-1, 0.16 vol %). Exfoliated graphene and polyacrylamide are microengineered to 3D composites such that conductive graphene pathways pervade the hydrogel matrix similar to an artificial nervous system. This makes it possible to combine both the exceptional conductivity of exfoliated graphene and the adaptable mechanical properties of polyacrylamide. The demonstrated approach is highly versatile regarding porosity, filler material, as well as hydrogel system. The important difference to other approaches is that we keep the original properties of the matrix, while ensuring conductivity through graphene-coated microchannels. This novel approach of generating conductive hydrogels is very promising, with particular applications in the fields of bioelectronics and biohybrid robotics

Wet-Chemical Assembly of 2D Nanomaterials into Lightweight, Microtube-Shaped, and Macroscopic 3D Networks

Despite tremendous efforts toward fabrication of three-dimensional macrostructures of two-dimensional (2D) materials, the existing approaches still lack sufficient control over microscopic (morphology, porosity, pore size) and macroscopic (shape, size) properties of the resulting structures. In this work, a facile fabrication method for the wet-chemical assembly of carbon 2D nanomaterials into macroscopic networks of interconnected, hollow microtubes is introduced. As demonstrated for electrochemically exfoliated graphene, graphene oxide, and reduced graphene oxide, the approach allows for the preparation of highly porous (> 99.9%) and lightweight (<2 mg cm-3) aeromaterials with tailored porosity and pore size as well as tailorable shape and size. The unique tubelike morphology with high aspect ratio enables ultralow-percolation-threshold graphene composites (0.03 S m-1, 0.05 vol%) which even outperform most of the carbon nanotube-based composites, as well as highly conductive aeronetworks (8 S m-1, 4 mg cm-3). On top of that, long-term compression cycling of the aeronetworks demonstrates remarkable mechanical stability over 10 000 cycles, even though no chemical cross-linking is employed. The developed strategy could pave the way for fabrication of various macrostructures of 2D nanomaterials with defined shape, size, as well as micro- and nanostructure, crucial for numerous applications such as batteries, supercapacitors, and filters

A Two-Dimensional Polyimide-Graphene Heterostructure with Ultra-fast Interlayer Charge Transfer

Two-dimensional polymers (2DPs) are a class of atomically/molecularly thin crystalline organic 2D materials. They are intriguing candidates for the development of unprecedented organic–inorganic 2D van der Waals heterostructures (vdWHs) with exotic physicochemical properties. In this work, we demonstrate the on-water surface synthesis of large-area (cm2), monolayer 2D polyimide (2DPI) with 3.1-nm lattice. Such 2DPI comprises metal-free porphyrin and perylene units linked by imide bonds. We further achieve a scalable synthesis of 2DPI-graphene (2DPI-G) vdWHs via a face-to-face co-assembly of graphene and 2DPI on the water surface. Remarkably, femtosecond transient absorption spectroscopy reveals an ultra-fast interlayer charge transfer (ca. 60 fs) in the resultant 2DPI-G vdWH upon protonation by acid, which is equivalent to that of the fastest reports among inorganic 2D vdWHs. Such large interlayer electronic coupling is ascribed to the interlayer cation–π interaction between 2DP and graphene. © 2021 The Authors. Angewandte Chemie International Edition published by Wiley-VCH Gmb

Ultrathin positively charged electrode skin for durable anion-intercalation battery chemistries

The anion-intercalation chemistries of graphite have the potential to construct batteries with promising energy and power breakthroughs. Here, we report the use of an ultrathin, positively charged two-dimensional poly(pyridinium salt) membrane (C2DP) as the graphite electrode skin to overcome the critical durability problem. Large-area C2DP enables the conformal coating on the graphite electrode, remarkably alleviating the electrolyte. Meanwhile, the dense face-on oriented single crystals with ultrathin thickness and cationic backbones allow C2DP with high anion-transport capability and selectivity. Such desirable anion-transport properties of C2DP prevent the cation/solvent co-intercalation into the graphite electrode and suppress the consequent structure collapse. An impressive PF6−-intercalation durability is demonstrated for the C2DP-covered graphite electrode, with capacity retention of 92.8% after 1000 cycles at 1 C and Coulombic efficiencies of > 99%. The feasibility of constructing artificial ion-regulating electrode skins with precisely customized two-dimensional polymers offers viable means to promote problematic battery chemistries

Ultrathin positively charged electrode skin for durable anion-intercalation battery chemistries

The anion-intercalation chemistries of graphite have the potential to construct batteries with promising energy and power breakthroughs. Here, we report the use of an ultrathin, positively charged two-dimensional poly(pyridinium salt) membrane (C2DP) as the graphite electrode skin to overcome the critical durability problem. Large-area C2DP enables the conformal coating on the graphite electrode, remarkably alleviating the electrolyte. Meanwhile, the dense face-on oriented single crystals with ultrathin thickness and cationic backbones allow C2DP with high anion-transport capability and selectivity. Such desirable anion-transport properties of C2DP prevent the cation/solvent co-intercalation into the graphite electrode and suppress the consequent structure collapse. An impressive PF6−-intercalation durability is demonstrated for the C2DP-covered graphite electrode, with capacity retention of 92.8% after 1000 cycles at 1 C and Coulombic efficiencies of &gt; 99%. The feasibility of constructing artificial ion-regulating electrode skins with precisely customized two-dimensional polymers offers viable means to promote problematic battery chemistries

A combinatorial study of electrochemical anion intercalation into graphite

Dual-ion batteries are considered to be an emerging viable energy storage technology owing to their safety, high power capability, low cost, and scalability. Intercalation of anions into a graphite positive electrode provides high operating voltage and improved energy density to such dual-ion batteries. In this work, we have performed a combinatorial study of graphite intercalation compounds considering four anions, namely hexafluorophosphate (PF ${}_{6}^{-}$ ), perchlorate (ClO ${}_{4}^{-}$ ), bis(fluorosulfonyl)imide (FSI ^− ), and bis(trifluoromethanesulfonyl)imide (TFSI ^− ), via first-principles calculations. The structural properties and energetics of the intercalation compounds are compared based on different sizes, geometries, and the physical and chemical properties of the intercalated anions. The staging mechanism of anion intercalation into graphite and the specific capacities, and voltage profiles of the intercalated compounds are investigated. A comparison regarding battery electrochemistry is also done with available experimental observations. Our calculated intercalation energies and voltage profiles show that the initial anion intercalation into graphite is less favorable than subsequent ones for all the anions considered in this study. Although the effect of the size of anions in a graphite cathode on various properties of the intercalated compounds is not as significant as the size of cations in a graphite anode, some distinction between the studied anions can still be made. Among the studied anions, the intercalation compounds based on PF ${}_{6}^{-}$ are the most stable ones. These PF ${}_{6}^{-}$ anions cause relatively small structural deformations of the graphite and have the highest oxidative ability, highest onset voltage, and highest diffusion barrier along the graphene sheets. The overall small diffusion barriers of the anions within graphite explain the high rate capability of dual-ion batteries

Carbon nanoparticles’ impact on processability and physical properties of epoxy resins : a comprehensive study covering rheological, electrical, thermo-mechanical, and fracture properties (mode I and II)

A trade-off between enhancement of physical properties of the final part and the processability during manufacturing always exists for the application of nanocarbon materials in thermoset-based composites. For different epoxy resins, this study elaborates the impact of nanocarbon particle type, functionalization, and filler loading on the resulting properties, i.e., rheological, electrical, thermo-mechanical, as well as the fracture toughness in mode I and mode II loading. Therefore, a comprehensive set of carbon nanoparticles, consisting of carbon black (CB), single-walled carbon nanotubes (SWCNT), multi-walled carbon nanotubes (MWCNT), few layer graphene (FLG), and electrochemically expanded graphite (ExG), in purified or functionalized configuration was introduced in various epoxy resins, with different molecular weight distributions. A novel technique to introduce sharp cracks into single-edge notched bending (SENB) fracture toughness specimens led to true values. SWCNT show highest potential for increasing electrical properties without an increase in viscosity. Functionalized MWCNT and planar particles significantly increase the fracture toughness in mode I by a factor of two